CN100367029C - Stannic oxide based nanometer rod air-sensitive material and process for preparing the same - Google Patents
Stannic oxide based nanometer rod air-sensitive material and process for preparing the same Download PDFInfo
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- CN100367029C CN100367029C CNB2005100351884A CN200510035188A CN100367029C CN 100367029 C CN100367029 C CN 100367029C CN B2005100351884 A CNB2005100351884 A CN B2005100351884A CN 200510035188 A CN200510035188 A CN 200510035188A CN 100367029 C CN100367029 C CN 100367029C
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- urea
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- stannic oxide
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Abstract
The present invention relates to the technical field of gas test or analysis with the aid of measuring the chemical or physical properties of a material. More specifically, the present invention relates to an electronic element material, particularly to a stannum dioxide based nanometer bar gas sensitive material and a preparing method thereof. The nanometer bar gas sensitive material is prepared through the steps that 1 part of tin tetrachloride, 1.5 to 3 parts of urea, and 0.08 to 0.12 part of bismuth nitrate are weighed according to a calculated molar ratio so as to realize material mixing; tin tetrachloride, urea and bismuth nitrate are stirred, dried, tableted and presintered. Compared with gas sensitive materials in the prior art, the stannum dioxide based nanometer bar gas sensitive material of the present invention has the advantages of simple technique and low cost; especially, resistive gas sensitive sensing elements made of the stannum dioxide based nanometer bar gas sensitive material have high sensitivity because the sensitivity value K in ethanol gas of 500 ppm reaches 29.2.
Description
Invention field
The present invention relates to by means of the chemistry of measuring material or physical property is tested or the technical field of analysis of material, specifically relate to a kind of materials of electronic components, particularly relate to a kind of tin ash (SnO
2) based nanometer rod air-sensitive material and preparation method.
Technical background
Because tin dioxide nano material has good gas-sensitive property, so be widely used in the gas sensor manufacturing industry.For sensitivity and selectivity, response speed and the release time of improveing this class sensor, the research work that the researcher did in the industry at present mainly is the following aspects: 1. make material granule thin as far as possible, preferably make nano material, increase the unit specific surface area, improve sensitivity; 2. gas sensitive is made film, so that the contact area of increase and gas improves sensitivity; 3. mix precious metal element or rare earth element, further improve the sensitivity and the selectivity of material.Although these methods can have been improved the gas-sensitive property of tin ash sill effectively, also exist complex process, the wayward and cost of microstructure is than problems such as height.In order further to improve the gas-sensitive property of stannic oxide based nanometer gas sensitive, the present inventor has submitted portion on November 5th, 2004 to State Intellectual Property Office, and (application number is: application for a patent for invention 200410052061.9) about " novel stannic oxide based nanometer gas sensitive and preparation method ".The major technique feature of this patented claim is to mix carbon nano-tube and be uniformly dispersed in the stannic oxide based nanometer powder that makes, thereby the microstructure of stannic oxide based nanometer gas sensitive is adjusted preferably, and sensitivity also increases significantly.The inventor is furtheing investigate discovery to the stannic oxide based nanometer gas sensitive of described novel stannic oxide based nanometer gas sensitive and the preparation of other method; its micromechanism all is connected to each other (referring to the Fig. 1) that forms by approaching spherical crystal grain; because spherical particle is not of uniform size; the porous ceramics that causes being produced contains a large amount of sealed porositys; thereby restricted the further lifting of further improvement, especially the sensitivity K value of its gas-sensitive property.
Development along with nanometer technology, preparation and the mechanism research about the nano material of bar-like grains growth at present more becomes focus, existing report adopts CNT and porous alumina formwork method, solution-liquid phase-solid phase (SLS) growth method, non-aqueous solvent thermal synthesis, laser ablation to combine growth method etc. with gas-liquid-solid (VLS) and produces various nanometer rods, but does not see the report of relevant nanometer rod air-sensitive material as yet.CSTINET issue on January 13rd, 2004 a piece of news, State Univ. of Singapore of Singapore (The National University of Singapore) successfully prepares tin ash (SnO2) nanometer rods, but this nanometer rods also only is applicable to and makes the Li-Ion rechargeable battery negative material.
Summary of the invention
The purpose of this invention is to provide a kind of stannic oxide based nanometer rod air-sensitive material, it is highly sensitive to use it to make the resistive gas sensor.
Another object of the present invention provides a kind of preparation method of above-mentioned stannic oxide based nanometer rod air-sensitive material.
It is composed of the following components that stannic oxide based nanometer rod air-sensitive material of the present invention is pressed net value mole (part) proportioning:
Butter of tin (SnCl
45H
2O) 1
Urea (H
2NCONH
2) 1.5～3
Bismuth nitrate (Bi (NO
3)
3) 0.08～0.12
Above-mentioned stannic oxide based nanometer rod air-sensitive material by net value mole (part) optimum ratio is:
Butter of tin (SnCl
45H
2O) 1
Urea (H
2NCONH
2) 1.5
Bismuth nitrate (Bi (NO
3)
3) 0.08
The method for preparing stannic oxide based nanometer rod air-sensitive material of the present invention is made up of the following step:
A) butter of tin is mixed according to the above ratio with urea, adding distil water is made into mixed solution, 80 ℃～95 ℃ stirred in water bath insulations, obtains the creaming thing;
B) bismuth nitrate is dissolved in rare nitric acid, dropping ammonia while stirring is until forming creaming;
C) two kinds of sediments of steps A and B gained are mixed mutually, use the deionized water cyclic washing, put into the drying box inner drying then;
D) dried particle is ground after, be pressed into sheet with dry powder press, 800～850 ℃ of annealing in process 1～3 hour, make the nanometer tin dioxide rod powder.
The invention described above stannic oxide based nanometer rod air-sensitive material preparation method is step D wherein) optimum annealing temperature be 820 ℃.
Because the present invention has added bismuth nitrate (Bi (NO) in raw material
3), and under 800～850 ℃ high temperature annealing in process, make bismuth nitrate can resolve into bismuth oxide (Bi
2O
3).In this process, one side Bi
2O
3Fully fusing forms liquid phase in sintering process, impels SnO
2The crystal grain different growth forms bar-like grains, Bi on the other hand
2O
3Be present in the air-sensitive powder as alloy, can improve sensitivity hydrocarbon class gas.The present invention has technology advantage simple, with low cost with respect to prior art, particularly uses it to make the sensitivity of resistive gas sensor up to 29.2.
Description of drawings:
The photo that Fig. 1 takes under scanning electron microscope at " the novel stannic oxide based nanometer gas sensitive " of first to file for the applicant;
The photo of Fig. 2 under scanning electron microscope, taking by the stannic oxide based nanometer rod air-sensitive material of the present invention of following embodiment 1 described proportioning and preparation method's preparation;
The photo of Fig. 3 under scanning electron microscope, taking by the stannic oxide based nanometer rod air-sensitive material of the present invention of following embodiment 2 described proportionings and preparation method's preparation.
Embodiment:
Example 1
By net value mole (part) than taking by weighing 1 part of butter of tin; 1.5 parts in urea; Behind 0.08 part of the bismuth nitrate by following step preparation:
A) butter of tin is mixed according to the above ratio with urea, adding distil water is made into mixed solution, 80 ℃ of (also can omit height a bit, but had better not above 95 ℃) stirred in water bath insulations, obtains the creaming thing;
B) bismuth nitrate is dissolved in rare nitric acid, dropping ammonia while stirring is until forming creaming;
C) two kinds of sediments of steps A and B gained are mixed mutually, use the deionized water cyclic washing, put into the drying box inner drying then;
D) dried particle is ground after, be pressed into sheet with dry powder press, 820 ℃ of annealing in process 2 hours, make tin ash bar-like grains nano-powder (its pattern as shown in Figure 2).
The resistive gas sensor that uses the present embodiment stannic oxide based nanometer rod air-sensitive material to produce, it is as shown in table 1 with the heating voltage running parameter to record (K Ω) value of resistance in air and the sensitivity in the 500ppm alcohol gas.
Table 1:
Example 2
Than taking by weighing 1 part of butter of tin, 3 parts in urea, behind 0.12 part of the bismuth nitrate, by example 1 identical step and order preparation, that different is step D by net value mole (part)) annealing temperature be 850 ℃, annealing time is 1 hour.The prepared tin ash rod-like nano morphology microstructure of present embodiment as shown in Figure 3.
The resistive gas sensor that uses the present embodiment stannic oxide based nanometer rod air-sensitive material to produce, it is as shown in table 2 with the heating voltage running parameter to record (K Ω) value of resistance in air and the sensitivity in the 500ppm alcohol gas.
Table 2:
Example 3
Than taking by weighing 1 part of butter of tin, 2 parts in urea, behind 0.1 part of the bismuth nitrate, by example 1 identical step and order preparation, that different is step D by net value mole (part)) annealing temperature be 800 ℃, annealing time is 3 hours.
The resistive gas sensor that uses the present embodiment stannic oxide based nanometer rod air-sensitive material to produce, it is as shown in table 3 with the heating voltage running parameter to record (K Ω) value of resistance in air and the sensitivity in the 500ppm alcohol gas.
Table 3:
Claims (4)
1. stannic oxide based nanometer rod air-sensitive material, this gas sensitive is made by net value molar part proportioning by following component:
Butter of tin SnCl
45H
2O 1
Urea H
2NCONH
21.5～3
Bismuth nitrate Bi (NO
3)
30.08～0.12
The preparation method of described gas sensitive is:
Earlier butter of tin is mixed in proportion with urea, adding distil water is made into mixed solution, 80 ℃～95 ℃ stirred in water bath insulations, obtains the creaming thing; Bismuth nitrate is dissolved in rare nitric acid, dropping ammonia while stirring is until forming creaming again; Then two kinds of sediments of preceding two step gained are mixed mutually, with putting into the drying box inner drying behind the deionized water cyclic washing; After at last dried particle being ground, be pressed into sheet, made in 1～3 hour 800～850 ℃ of annealing in process with dry powder press.
2. a kind of stannic oxide based nanometer rod air-sensitive material according to claim 1, each component by net value molar part proportioning is:
Butter of tin SnCl
45H
2O 1
Urea H
2NCONH
21.5
Bismuth nitrate Bi (NO
3)
30.08.
3. the preparation method of a tin-dioxide-base composite nano rod air-sensitive material as claimed in claim 1 or 2 is made up of the following step:
A) butter of tin is mixed in proportion with urea, adding distil water is made into mixed solution, 80 ℃～95 ℃ stirred in water bath insulations, obtains the creaming thing;
B) bismuth nitrate is dissolved in rare nitric acid, dropping ammonia while stirring is until forming creaming;
C) two kinds of sediments of steps A and B gained are mixed mutually, use the deionized water cyclic washing, put into the drying box inner drying then;
D) dried particle is ground after, be pressed into sheet with dry powder press, 800～850 ℃ of annealing in process 1～3 hour, make the nanometer tin dioxide rod powder.
4. a kind of stannic oxide based nanometer rod air-sensitive material preparation method according to claim 3, wherein step D) annealing temperature be 820 ℃.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100405049C (en) * | 2006-04-18 | 2008-07-23 | 云南大学 | Gas sensor made of SnO2 cluster nano-rod |
| CN100354208C (en) * | 2006-07-17 | 2007-12-12 | 华东理工大学 | Prepn process of nanometer tin dioxide rod |
| CN101298338B (en) * | 2008-04-21 | 2010-04-14 | 上海大学 | Electron beam radiation synthetic method of stannic oxide nano-rod |
| CN102408125B (en) * | 2011-08-06 | 2013-07-24 | 深圳市德厚科技有限公司 | Preparation method of bismuth-doped tin dioxide nanopowder |
| CN102507657A (en) * | 2011-11-08 | 2012-06-20 | 中南大学 | Method for preparing high-sensitivity bismuth-doped tin dioxide sensing material |
| CN106430293A (en) * | 2016-09-28 | 2017-02-22 | 沪本新材料科技（上海）有限公司 | Preparation method of novel bismuth-doped tin dioxide powder with high near-infrared reflectivity |
| CN108217717B (en) * | 2017-12-19 | 2020-02-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Mn-doped tin dioxide gas-sensitive material, product and application thereof |
| CN110117027B (en) * | 2019-05-28 | 2021-08-24 | 北华航天工业学院 | SnO (stannic oxide)2Nano-rod and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030067003A1 (en) * | 2001-09-28 | 2003-04-10 | Gole James L. | Tin oxide nanostructures |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030067003A1 (en) * | 2001-09-28 | 2003-04-10 | Gole James L. | Tin oxide nanostructures |
Non-Patent Citations (4)
| Title |
|---|
| Rapid synthesis of nanocrystalline SnO2 powders bymicrowave heating method. Jun-Jie Zhu, et al.Materials Letters,Vol.53 No.3. 2002 * |
| SnO2气敏元件中无机粘接剂的作用和影响. 吕平，傅刚，陈环，丁志文.传感器技术，第23卷第6期. 2004 * |
| SnO2纳米棒的制备及表征. 侯德东，刘应开.无机材料学报，第17卷第4期. 2002 * |
| 掺杂Bi2O3及Sb2O3的SnO2陶瓷气敏性研究. 张循海，林蔚，唐万侠，丁莹莹.齐齐哈尔大学学报，第18卷第2期. 2002 * |
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